Reaction product of naphtholactams and indole derivatives as dyestuffs



United States latent ()fidce 3,320,279 Patented May 16, 196? The presentinvention relates to novel dyestuffs; more particularly it relates todyestuffs of the formula in this formula R stands for hydrogen or analkyl, aralkyl, cycloalkyl or aryl radical, R R and R stand for loweralkyl groups; X represents an acid radical used for salt formation ofbasic dyestuffs, and the aromatic rings as well as the radicals R and RR and R may contain non-ionic substituents.

The new dyestuffs are obtained by reacting compounds of the generalformula wherein R has the above-indicated meaning, and wherein thenaphthalene rings may contain one or two nonionic substituents, with.indole derivatives of the general formula wherein R R and R have theabove meaning and where in the nucleus may contain non-ionicsubstiuents, and in the case where naphtholactam components (I) are usedwherein R stands for hydrogen, the dyestuffs obtained in the form of thesalts, are optionally converted into the corresponding bases and theseare treated with quaternising agents R'X, wherein R means alkyl, aralkylor cycloalkyl.

Examples of non-ionic substituents with which the dyestuffes may befurther substituted are halogen atoms such as fluorine, chlorine andbromine, lower alkyl and lower alkoxy groups such as methyl, ethyl,isopropyl, methoxy and ethoxy groups, and nitro and amino groups, acylradicals and sulphonamide groups as well as non-ionic derivatives ofcarboxylic acid groups, such as carboxylic ester, carboxylic amide, andnitrile groups.

For carrying out the process for manufacture of the novel dyestufls thereaction components (I) and (H) are heated in an inert diluent, such asbenzene, toluene, chloroform, carbon tetrachloride, ethylene chloride,chlorobenzene, dichlorobenzene, dioxan or nitrobenzene, and an agent forsplitting off water is added. As such the principal suitable examplesare acid chlorides, such as phosphorus oxychloride, phosphorustrichloride, phosphorus pentachloride, thionyl and sulphuryl chlorides,phosgene or mixtures thereof. It is frequently advantageous to addFriedel-Crafts catalysts, such as aluminum chloride, zinc chloride,stannic chloride, ferric chloride or boron trifluoride. In general thereaction is conducted at temperatures between 20 and 150 C., butpreferably between 60 and 130 C.

If component (I) is used in which R stands for hydrogen, the subsequentquaternisation of the dyestuffs obtained as salts, is expedientlyperformed by dissolving the salts in a suitable solvent, such as wateror alcohol, mixing the solution with excess alkaline agents, for examplewith aqueous or alcoholic caustic soda, caustic potash, soda or ammonia,isolating the separated dyestuff base, drying it in the usual way, thendissolving it in a dry solvent, e.g. in benzene, toluene, chloroform,sym.-tetrachloroethane or dimethyl formamide, and treating this solutionat a temperature between 60 to 150 0., preferably to 130 C., with aquaternising agent, for example with dimethyl sulphate, diethylsulphate, p-toluenesulphonic acid methyl ester or methyl iodide Suitablecompounds of the general Formula I are, for example, naphtholactam 1,8),4-chloro-naphtholactam- (1,8) 4 bromo-naphtholactam-( 1,8)2,4-dichloro-naphtholactam-( 1,8) N-methyl-naphtholactam-( 1,8)N-ethyl-naphtholactam-( 1,8), N-n-propylor N-isoamyl-naphtholactam-( 1,8N-benZyl-naphtho1actam-( 1,8) N -phenyl naphtholactam (1,8),N-ethyl-4-chloro-naphtholactam (1,8), N-ethyl-4-bromoorN-ethyl-4-acetyl-naphtholactam (1,8),N-ethyl-4-dimethylamino-naphtholactam- 1,8) andN-methyl-4-phenylazo-nahtholactam-( 1,8).

Suitable compounds (11) are, for example, 1,3,3-trimethyl wcyano-2-methylene-S-methoxy-dihydro-(2,3)- indole, 1,3,3 trimethyl wcyano-Z-methylene-dihydro- (2,3)-indole, 1,3,3 trimethyl wcyano-Z-methylene-S- chloro-dihydro-(2,3)-indole and1,3,3-trimethyl-w-cyano- Z-methylene-dihydro- (2,3 -indole-5-carboxylicacid methyl ester.

The new dyestuffs are suitable for the dyeing, printing and bulk dyeingof synthetic or semi-synthetic materials, eg. synthetic superpolyamides,and acetate rayon, cellulose materials such as paper, for the dyeing ofleather as well as for application in rubber printing, for theproduction of writing pastes and fluids, but especially for the dyeing,printing and spin-dyeing of materials which consist wholly orpredominantly of polymerised acrylonitrile and/or vinylidene cyanide.The dyeings and prints on the last-mentioned materials are distinguishedby outstanding fastness properties, in particular fastness to light,washing, sublimation and decatising. The new dyestuffs possess a goodaffinity for these materials and yield deep shades.

The following examples are given for the purpose of illustrating theinvention without, however, limiting it thereto; the parts given areparts by weight.

Example 1 22.8 parts of 1,3,3-trimethyl-w-cyano-2-methylene-5-methoxy-dihydro-(2,3)-indole and 18.3 parts of N-methyl-naphtholactam-(1,8) are heated to C. with parts of chlorobenzene and mixed with 20parts of phosphorus oxychloride. Stirring is continued to the end of theevolution of hydrogen chloride at 100-110 C. and the chlorobenzene isthen distilled off under reduced pressure. The residue is recrystallisedfrom 1000 parts of water with addition of charcoal. By salting out thefiltrate, the dyestuff of the following formula is obtained:

CHs-C OCHa ('3 I ON 1? CH3 which gives outstandingly light-fast violetdyeings and prints on polyacrylonitrile.

which dyes polyacrylonitrile in bluish-red shades. By treatment withalkalies, such as sodium hydroxide, soda or ammonia, the correspondingfree base is obtained in the usual way, of the formula CHs-C GCH3 with amelting point of 218 C. t

13.6 parts of this base are dissolved in 200 parts of benzene, 5 partsof dimethyl sulphate are added at 75 C., and the mixture is boiled for45 minutes. The methosulphate corresponding to the dyestufi of Example 1separates out.

Instead of the benzene, toluene of chlorbenzene, for example, can alsobe used as solvent for the dye base.

Example 3 19.8 parts of1,3,3-trimethyl-w-cyano-2-methylene-dihydro-(2,3)-indole and 19.7 partsof N-ethyl-naphtholactam-(1,8) are heated to 120 C. with 150 parts ofchlorobenzene. 20 parts of phosphorus oxychloride are added dropwise,the temperature is maintained at 110- 120 C. for 5 hours, thechlorobenzene is removed in vacuum and the residue crystallised from1000 parts of water with addition of charcoal. The dyestuff of thefollowing formula is obtained which dyes polyacrylonitrile in red-violetshades.

4 Example 4 19.8 parts of1,3,3-trimethyl-w-cyano-Z-methyIene-dihydro-(2,3)-indole and 17.0 partsof naphtholactam- (1,8) are stirred for one hour under reflux with 150parts of ethylene chloride and 20 parts of phosphorus oxychloride. Afterdistilling off the ethylene chloride and the excess phosphorusoxychloride, the dyestuif of the following formula is obtained whichdyes polyacrylonitrile in bluish red shades. The corresponding free baseof the formula CHa-C melts at 191 C. Upon treatment with dimethylsulphate it yields the dyestuif of the formula GHQ-C OKs-N 11}- C: G

and with diethyl sulphate the ethyl sulphuric acid salt corresponding tothe dyestuif of Example 3.

Example 5 6 parts of1,3,3-trimethyl-w-cyano-2-methylene-S-methoxy-d-ihydro-(2,3)-indole and6 parts of 4-dimethylamin0- N-ethyl-naphtholac-tam-(1,8) are stirredwith 35 parts of phosphorus oxychloride for minutes at 55-60 C. Thephosphorus oxychloride is then removed under reduced pressure, theresidue dissolved in parts of water and the solution neutralised with adilute sodium hydroxide or sodium carbonate solution. The dyestufi thusobtained can be purified by recrystallisation from water and correspondsto the formula NCH:

It dyes polyacrylonitrile in greenish blue shades.

6 If the equilavent amount of 4-bromo-N-ethyl naphtho- 3. The dyestulfof the formula lactam is used instead of the dimethylamino-N-ethyl OH 3naphtholactam, the dyestufi of the formula UHF OCH:

5H: 5 OH: OCH: H N I I l 39% C2H51|\I|C=?\N CH;

N C (L1H; C1 10 Br 4. The dyestuff of the formula Br is obtained whichdyes polyacrylonitrile in reddish blue 5 H3 shades.

I claim: 1. A dyestufl of the formula C2H5 N C \N/ C1- R ON I Rg-TRNC=CC l I I 5. The dyestuff of the formula B I M 0H: We CH3 wherein Rstands for a member selected from the group T 01 consisting of hydrogen,lower alkyl, benzyl and phenyl; ON (ljHa R R and R stand for a loweralkyl; X stands for the residue of an acid used for salt formation ofbasic dyestuffs; A stands for a member selected from the groupconsisting of hydrogen, chlorine, bromine, methyl, ethyl, loweralkyl-substituted amino, and phenylazo; B stands References Cited by theExammer for a member selected from the group consisting of hy- UNITEDSTATES PATENTS drogen, methoxy, ethoxy, chlor1ne, bro:mme, and carbo3,090,782 5/1963 Coenen et a1 26O 240 6 lower alkoxy, and n stands foran integer ranging from 1 to 2. OTHER REFERENCES 2. The dyestulf of theformula Ficken et al.: J. Chem. Soc., 1960, pages 1529 to 1532 and 1535to'1541.

Chemical Abstracts, volume 52, column 11427 (1958) (abstract ofDokunikhin et al.). JOHN RANDOLPH, Primary Examiner,

an! I I UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent Noa 3,320, 279 May 16, 1967 Alfred Brack It is hereby certified that errorappears in the above numbered patent requiring correction and that thesaid Letters Patent should read as corrected below.

Column 1, line 57, "dyestuffes" read dyestuffs column 2, line 34, for"nahtholactam" read naphtholactam column 3, lines 37 to 46, for theright-hand portion of the formula reading CCH read OCH column 5, line 1,for "equilavent" read equivalent "a Signed and sealed this 28th day ofNovember 1967 (SEAL) Attest:

Edward M. Fletcher, Jr. EDWARD J BRENNER Attesting Officer Commissionerof Patents

1. A DYESTUFF OF THE FORMULA
 2. THE DYESTUFF OF THE FORMULA